Bridged halotriazine compounds as bleach activators

ABSTRACT

Bridged halotriazine compounds of the formula   WHERE A represents a group selected from vinylene, phenylene, biphenylene, stilbyl and ethynylenebis(p-phenylene) groups; Z represents a group selected from -O-, -S- or -N(H)-; n is an integer selected from zero and one; X1 and X2 individually represent chlorine, bromine or fluorine; and R1 and R2 individually represent halogen, hydroxy, mercapto, alkyl, alkenyl, alkoxy, alkylmercapto, aryl, aryloxy, arylmercapto, dialkoxyphosphinyl or   WHERE R3 and R4 may be hydrogen, alkyl, cyanoalkyl, hydroxyalkyl, carboxyalkyl, chloroalkyl, alkoxyalkyl, sulfoalkyl, aryl, sulfoaryl, acylaminoaryl or carbamoylalkyl, or where R3 and R4 taken together may be joined to complete a heterocyclic ring selected from morpholine, piperazine and piperidine rings; are effective as bleach activators for peroxygen bleaching compositions.

United States Patent 1 Loffelman et a].

[ 1 Sept. 23, 1975 1 BRIDGED HALOTRIAZINE COMPOUNDS AS BLEACH ACTIVATORS [75] Inventors: Frank Fred Loffelman, Somerville;

Thomas Eugene Brady, Piscataway, both of NJ.

[73] Assignee: American Cyanamid Company,

Stamford, Conn.

22 Filed: Mar. 21, 1973 211 Appl. No.: 343,576

[52] U.S. Cl. 252/99; 252/102; 252/186; 252/543 [51] Int. Cl. ...C11D 3/26; C1 1D 7/32; C11D 7/38; COlB 15/00 [58] Field of Search 252/543, 186,95, 99, 102; 8/111; 260/248 CS [56] References Cited UNITED STATES PATENTS 2,763,650 9/1956 Ackermann 252/99 X 2,956,898 10/1960 Fleck 8/111 X 3,704,228 11/1972 Eckert et a1.. 252/117 3,741,903 6/1973 Evans v. 252/95 Primary Examiner-Benjamin R. Padgett Assistant Examiner-Christine M. Nucker Attorney, Agent, or Firm-John L. Sullivan [57] ABSTRACT Bridged halotriazine compounds of the formula where R, and R may be hydrogen, alkyl, cyanoalkyl, hydroxyalkyl, carboxyalkyl, chloroalkyl, alkoxyalkyl, sulfoalkyl, aryl, sulfoaryl, acylaminoaryl or carbamoylalkyl, or where R and R taken together may be joined to complete a heterocyclic ring selected from morpholine. piperazine and piperidine rings; are effective as bleach activators for peroxygen bleaching compositions.

6 Claims, N0 Drawings BRIDGED HALOTRIAZINE COMPOUNDS AS BLEACH ACTIVATORS This invention relates to bleaching compositions and more particularly to improved bleaching compositions comprising hydrogen peroxide or hydrogen peroxidereleasing compound and as an activator for the peroxide-releasing compound a bridged halotriazine represented by the formula:

where A represents a group selected from vinylene, phenylene, biphenylene, stilbyl and ethynylenebis(pphenylene) groups; Z represents a group selected from -O, S- or N(H)-; n is an integer selected from zero and one; X and X individually represent chlorine, bromine or fluorine; and R and R individually represent halogen, hydroxy, mercapto, alkyl, alkenyl, alkoxy, alkylmercapto, aryl, aryloxy, arylmercapto, dialkoxyphosphinyl or Cl- -NH- "1 Y NQ/N where R and R are as defined in formula I, above.

As illustrative of compounds which can be used as activators in the bleach compositions of the present invention, there may be mentioned the following.

so r:

W 5 osc- Y scan CHaO-fw Kym H Cla CH- -cl N(CH CH OH) N(CH CH OH) The bleaching compositions of the invention contain the activating compound and the hydrogen peroxidereleasing compound in a molar ratio ranging from about lzl tov about 1210, respectively, with a preferred range of about 1:1 to 1:3. The actual ratio of activator to bleach can, of course, be varied widely for varying applications. I

The. oxygen bleaches useful in these bleaching compositions are hydrogen peroxide and organic peroxides and inorganic peroxygen salts that liberate hydrogen peroxide in water. Examples of peroxide bleaching compounds are urea peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, and the like. Examples of inorganic peroxygen bleaching compounds are alkali metal perborates, percarbonates, perphosphates, persulfates, monopersulfates, and the like. Mixtures of two or more bleaching compounds can, of course, beused if desired. 7

Although the various peroxide releasing compounds as mentioned above may be used in the compositions of the invention, preferred peroxide-releasing compounds are sodium perborate (for economic considerations) and sodium percarbonate (for ecological considerations).

The activated bleach compositions of the invention are useful for bleach applications for various substrates including fabrics, particularly when'incorporated with detergent compositions for household or commercial laundering purposes. A most important property of such detergent compositions is the ability to remove stains including food stains such as those of coffee, tea, wine and the like as well as to maintain purity of white in uncolored textiles. Aside from food stains, soiling in general may be removed such as grass stains, urine stains and the like.

In addition to the detergent, peroxygen-releasing compound and peroxygen bleach activator, such detergent compositions may contain other optional additives such as germicides, fungicides, enzymes, optical brighteners, colorants, perfumes, thickeners, emulsion or suspension stabilizers, and the like, including builders, such as sodium phosphate, salts, carbonates, silicates, and the like as usually encountered in the art.

The detergent component of such activated bleach compositions may be any of the conventional types such as anionic, cationic, nonionic or amphoteric.

Examples of typically suitable anionic detergents include the alkali metal or alkaline earth metal salts of higher alkylbenzene sulfonates, olefin sulfonates, higher alkyl sulfates and higher fatty acid monoglyceride sulfates.

Examples of typically suitable cationic detergents include tetraalkyl ammonium salts in which one of the alkyl groups contains approximately 12 to 18 carbons such as dodecyltrimethylammonium chloride or ethyldimethyloctadecylammonium methosulfate.

Examples of suitably typical amphoteric detergents are those detergent compounds possessing both cationic and anionic sites and include, for example, amino fatty acids such as dimethylaminopropionic acid and iminodifatty acids such as methyliminodilauric acid.

Examples of typical nonionic detergents include polyglycol ethers of alkanol amides of higher fatty acids and also polyglycol-ethers of higher alkanols and higher fatty acids.

Bleaching compositions may generally be used also for their germicidal properties in various applications for control of microbial growth. Applications may be made to any surface or substrate where such control is desired.

The treatment of swimming pool water and swimming pool surfaces with the compositions of the invention is especially efficacious since the usually lower temperatures of these environments prevent effective use of other antimicrobial agents. A related utility is the treatment of water supplies to render the same fit for human consumption or for industrial use, such as the sanitization of field water for consumption by military personnel or the treatment of industrial process water so it can be reused in industrial processes or by the surrounding community. The compositions also may be employed in admixture with detergents for use as home or industrial germicidal detergents, or in hair bleaching compositions containing peroxygen compounds.

The following examples and tests will serve to illustrate the invention.

EXAMPLES l and 2 Evaluation of Compounds as Bleach Activators Representative bridged halotriazine compounds of the invention were evaluated as bleach activators applied with sodium perborate and a detergent. In the evaluation tests, the mole ratio of activator used to sodium perborate was 1:1.1, although a lesser amount of activator was also tested.

The test procedure was as follows: Five-gram swatches of desized, 80 X 80 cotton fabric are stained with tea in the following manner. Five tea bags are 5 before and after laundering using a Hunter Model 25-M Reflectometer with a blue filter. The swatches are backed with a white procelain plate and read once on each side. Fluorescent effect is excluded from all readings.

The reflectance readings are averaged and the pera cent stain removal is obtained in accordance with the following formula in which R is the symbol for Reflectance:

R (bleached) minus R (stained) Total Stam removal: R (unstained) minus R (stained) Control runs are also made foreach set or'series of evaluation tests using detergent and sodium perborate r with nolactivator. The percent stain removed may vary somewhat on the Control due to variations in the cloth and the tea used to produce the stains.

The test results obtained are shown in Table I wherein the activator compounds tested are identified by the R and R radicals thereof in the general formula shown at the top of the Table.

TABLE I H 01- I -N- ca=cn- N T 03H 7c Stain Removed Wgt. of Activator Ex. No. R R2 (Control) (g.) Stain Removed 1 -N-H NH 35.9 2.50 45.5 .50 42.8

2 -ocH., -0CH 35.9 2.50 55.6 .50 40.4

placed in one liter of water and boiled for five minutes. We claim:

The swatches are then immersed in the tea and the boiling is continued for another five minutes. The swatches are then removed from the tea, wrung out, dried at 2002l5F., rinsed in cold water and again dried.

Two of the stained cotton swatches are placed in a stainless steel Terg-O-Tometer, a test washing machine, manufactured by U.S. Testing Company and used in the detergent trade for evaluation purposes. Forty grams of unstained cotton fabric and one liter of distilled water at F. are then added so as to provide a typical household washing machine water to cloth ratio of about 20:1. There are then added 2.0 grams of Tide (an anionic alkylaryl sulfonate type detergent), 0.33 gram of anhydrous sodium perborate (or an equivalent of hydrated material) and the indicated amount of the activator compound. The Terg-O-Tometer is op- 1. An activated bleaching composition comprising hydrogen peroxide or a hydrogen peroxide-releasing compound and an activating amount of a bridged halo triazine compound represented by the formula:

where R and R may be hydrogen, cyanoalkyl, carboxyalkyl, ehloroalkyl, alkoxyalkyl, sulfoalkyl, aryl, sulfoaryl, acylaminoaryl or carbamoylalkyl, or where R; and R taken together may be joined to complete a heterocyclic ring selected from morpholine, piperazine and piperidine rings.

2. A composition according to claim 1 wherein the mole ratio of the bridged halotriazine compound to the hydrogen peroxide-releasing compound is from about 1:1 to about 1:10,

3. A composition according to claim 1 wherein the hydrogen peroxide-releasing compound is sodium perborate or sodium percarbonate.

4. A composition according to claim 3 wherein the bridged halotriazine compound is represented by the formula 5. A composition according to claim 3 wherein the bridged halotriazine compound is represented by the 1H3 EH 6. A composition according to claim 1 containing a detergent. 

1. AN ACTIVATED BLEACHING COMPOSITION COMPRISING HYDROGEN PEROXIDE OR A HYDROGEN PEROXIDE-RELEASING COMPOUND AND AN ACTIVATING AMOUNT OF A BRIDGED HALO TRIAZINE COMPOUND REPRESENTED BY THE FROMULA:
 2. A composition according to claim 1 wherein the mole ratio of the bridged halotriazine compound to the hydrogen peroxide-releasing compound is from about 1:1 to about 1:10.
 3. A composition according to claim 1 wherein the hydrogen peroxide-releasing compound is sodium perborate or sodium percarbonate.
 4. A composition according to claim 3 wherein the bridged halotriazine compound is represented by the formula
 5. A composition according to claim 3 wherein the bridged halotriazine compound is represented by the formula
 6. A composition according to claim 1 containing a detergent. 